JPH02279666A - Production of carbamate and its intermediate - Google Patents
Production of carbamate and its intermediateInfo
- Publication number
- JPH02279666A JPH02279666A JP2056796A JP5679690A JPH02279666A JP H02279666 A JPH02279666 A JP H02279666A JP 2056796 A JP2056796 A JP 2056796A JP 5679690 A JP5679690 A JP 5679690A JP H02279666 A JPH02279666 A JP H02279666A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- alkali metal
- atom
- metal salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 title 1
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- -1 alkali metal salt Chemical class 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 15
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 239000012442 inert solvent Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 150000004678 hydrides Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 239000002917 insecticide Substances 0.000 abstract description 6
- TWVMOBWHILUBSS-UHFFFAOYSA-N benzoylcarbamic acid Chemical compound OC(=O)NC(=O)C1=CC=CC=C1 TWVMOBWHILUBSS-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000749 insecticidal effect Effects 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000003129 miticidal effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 8
- 239000012312 sodium hydride Substances 0.000 description 8
- 229910000104 sodium hydride Inorganic materials 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000004280 Sodium formate Substances 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 5
- 235000019254 sodium formate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 3
- KTXFXDMDYZIXSJ-UHFFFAOYSA-N 2,4-difluorobenzamide Chemical compound NC(=O)C1=CC=C(F)C=C1F KTXFXDMDYZIXSJ-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 229940054066 benzamide antipsychotics Drugs 0.000 description 2
- 150000003936 benzamides Chemical class 0.000 description 2
- LURYMYITPCOQAU-UHFFFAOYSA-N benzoyl isocyanate Chemical compound O=C=NC(=O)C1=CC=CC=C1 LURYMYITPCOQAU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- DWLVWMUCHSLGSU-UHFFFAOYSA-M n,n-dimethylcarbamate Chemical compound CN(C)C([O-])=O DWLVWMUCHSLGSU-UHFFFAOYSA-M 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CJDWRQLODFKPEL-UHFFFAOYSA-N teflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC(Cl)=C(F)C(Cl)=C1F CJDWRQLODFKPEL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GXHSCFXDSHCSNW-UHFFFAOYSA-N 2,6-dichloro-n-[(3,4-dichlorophenyl)carbamoyl]benzamide Chemical compound C1=C(Cl)C(Cl)=CC=C1NC(=O)NC(=O)C1=C(Cl)C=CC=C1Cl GXHSCFXDSHCSNW-UHFFFAOYSA-N 0.000 description 1
- JTHMHWAHAKLCKT-UHFFFAOYSA-N 2,6-difluoro-n-[[4-(trifluoromethyl)phenyl]carbamoyl]benzamide Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(C(F)(F)F)C=C1 JTHMHWAHAKLCKT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 108700018454 CDC15 Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005893 Diflubenzuron Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000272168 Laridae Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000277269 Oncorhynchus masou Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000005938 Teflubenzuron Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 101150081467 cdc15 gene Proteins 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QQQYTWIFVNKMRW-UHFFFAOYSA-N diflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C=C1 QQQYTWIFVNKMRW-UHFFFAOYSA-N 0.000 description 1
- 229940019503 diflubenzuron Drugs 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- RYLHNOVXKPXDIP-UHFFFAOYSA-N flufenoxuron Chemical compound C=1C=C(NC(=O)NC(=O)C=2C(=CC=CC=2F)F)C(F)=CC=1OC1=CC=C(C(F)(F)F)C=C1Cl RYLHNOVXKPXDIP-UHFFFAOYSA-N 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- TZXQHGFQXBLNCD-UHFFFAOYSA-N n-(hydroxyamino)-n-phenylhydroxylamine Chemical group ONN(O)C1=CC=CC=C1 TZXQHGFQXBLNCD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/18—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by doubly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/62—Compounds containing any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylcarbamates
- C07C271/64—Y being a hydrogen or a carbon atom, e.g. benzoylcarbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野〕
本発明は、カルバメート、特にN−ベンゾイルカルバメ
ートの製造方法、およびこの製造における中間体に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing carbamates, particularly N-benzoyl carbamates, and to intermediates in this production.
英−特許第1,324,293号公報は、式〔式中、M
はリチウム、ナトリウムもしくはカリウム原子であり、
かつR1、R1、RsおよびRは請求項1〜4のいずれ
か一項に記載の意味を有する〕
のN−ベンゾイルカルバメートのアルカリ金属塩。British Patent No. 1,324,293 discloses the formula [where M
is a lithium, sodium or potassium atom,
and R1, R1, Rs and R have the meanings according to any one of claims 1 to 4]. An alkali metal salt of N-benzoyl carbamate.
C式中、Aは水素原子、ハロゲン原子、メチル基もしく
はメトキシ基であり、Bは水素原子、ハロゲン原子、メ
チル基もしくはメトキシ基を示し、ただしAおよびBは
両者ともには水素原子を示さず、XおよびYは両者とも
酸素原子とすることができ、RおよびR7は両者とも水
素原子とすることができ、かつR8は特に置換フェニル
基を示す〕
を有する種類の化合物、および殺虫剤としてのその使用
を開示している。In formula C, A is a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and B represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, provided that both A and B do not represent a hydrogen atom, X and Y can both be oxygen atoms, R and R can both be hydrogen atoms, and R8 especially represents a substituted phenyl group], and the same as insecticides. Use is disclosed.
AおよびBが両者とも弗素原子であり、XおよびYが両
者とも酸素原子であり、RおよびRtが両者とも水素原
子であり、かつR1が4−クロルフェニルである上記式
の化合物は殺虫剤ジフルベンズロン[N−(4−クロル
フェニル)−N’−(2゜6−ジフルオロベンゾイル)
尿素1であり、またR、が4−トリフルオロメチルフェ
ニルである対応の化合物は殺虫剤ペンフルロン[N−(
2,6−ジフルオロベンゾイル)−N’−(4−)リフ
ルオロメチルフェニル)尿素1である。米国特許第4.
457.943号公報は、特にN−(2,4−ジフルオ
ロ−3,5−ジクロルフェニル)−N’−(2,6−ジ
フルオロベンゾイル)尿素、すなわちテフルベンズロン
として知られた殺虫剤を開示している。The compound of the above formula in which A and B are both fluorine atoms, X and Y are both oxygen atoms, R and Rt are both hydrogen atoms, and R1 is 4-chlorophenyl is an insecticide diflubenzuron. [N-(4-chlorophenyl)-N'-(2゜6-difluorobenzoyl)
The corresponding compound in which urea is 1 and R is 4-trifluoromethylphenyl is the insecticide penfluron [N-(
2,6-difluorobenzoyl)-N'-(4-)lifluoromethylphenyl)urea 1. U.S. Patent No. 4.
No. 457.943 discloses, inter alia, an insecticide known as N-(2,4-difluoro-3,5-dichlorophenyl)-N'-(2,6-difluorobenzoyl)urea, i.e. teflubenzuron. ing.
ヨーロッパ特許出11EP−A−161019号公報は
、特にN−(2,6−ジフルオロベンゾイル)−N’−
(2−フルオロ−4−R2−クロル−4−(トリフルオ
ロメチル)フェノキシ1フエニル尿素、すなわちフルフ
ェノクスロンとして知られた殺虫剤/殺ダニ剤を開示し
ている。European Patent Publication No. 11EP-A-161019 specifically describes N-(2,6-difluorobenzoyl)-N'-
(2-Fluoro-4-R2-chloro-4-(trifluoromethyl)phenoxy1phenylurea, an insecticide/acaricide known as flufenoxuron).
RおよびRtが両者とも水素である上記式の化合物を製
造するため英国特許第1,324,293号に提案され
た一つの方法は、式
の0−エチルカルバメート化合物を式R,−N)i。One method proposed in British Patent No. 1,324,293 for preparing compounds of the above formula in which R and Rt are both hydrogen is to convert an 0-ethyl carbamate compound of the formula R, -N)i .
の化合物と反応させることからなっている〔第11頁、
第13〜18行〕、この反応は溶剤の存在下で行なわれ
ると記載されている〔第14頁、第25〜29行〕、適
する溶剤の例はキシレン、トルエン、クロルベンゼンお
よびその他の同様な約100℃より高い沸点を有する溶
剤である0反応は、使用する溶剤の沸点にほぼ等しい温
度で行なわれる。その実施例10は、溶剤としてキシレ
ンを用い、収率90%でN−(2,6−ジクロルベンゾ
イル)−N’−(3,4−ジクロルフェニル)尿素をこ
のように製造することを記載している。0−エチルカル
バメートの製造については記載がない。[Page 11,
lines 13-18], the reaction is stated to be carried out in the presence of a solvent [page 14, lines 25-29], examples of suitable solvents being xylene, toluene, chlorobenzene and other similar Solvents with a boiling point above about 100° C. reactions are carried out at a temperature approximately equal to the boiling point of the solvent used. Example 10 thereof demonstrates the preparation of N-(2,6-dichlorobenzoyl)-N'-(3,4-dichlorophenyl)urea in this way with a yield of 90% using xylene as the solvent. It is listed. There is no description of the production of 0-ethyl carbamate.
ヨーロッパ特許出願EP−A−174274号およびE
P−A−219460号、並びに英国特許出願CB−A
−2163430号公報は全て、N−ベンゾイルカルバ
メートの種類および適する置換アニリンとの反応により
殺虫活性を有する各種のN−ベンゾイル−N−フェニル
尿素を製造する際のその使用を開示している。たとえば
、英国特許出IGB−A−2163430号公報は、式
〔式中、R1は水素、ハロゲン、CF、もしくはCI−
4アルコキシであり、R虐はハロゲン、C1−4アルキ
ル、CFsもしくはC1−4アルコキシであり、R3は
水素、ハロゲン、CFIもしくはメチルであり、かつR
はC1−アルキル基であって゛ハロゲン(好ましくは塩
素)により置換することができる)
のN−ベンゾイル−カルバメートを開示している。European patent applications EP-A-174274 and E
P-A-219460 and British patent application CB-A
JP-A-2163430 all disclose types of N-benzoyl carbamates and their use in preparing various N-benzoyl-N-phenylureas having insecticidal activity by reaction with suitable substituted anilines. For example, British Patent Publication No. IGB-A-2163430 describes the formula [wherein R1 is hydrogen, halogen, CF, or CI-
4 alkoxy, R is halogen, C1-4 alkyl, CFs or C1-4 alkoxy, R3 is hydrogen, halogen, CFI or methyl, and R
discloses N-benzoyl-carbamates of C1-alkyl groups which can be substituted by halogen (preferably chlorine).
これらpN−ベンゾイル−カルバメートは、適するベン
ゾイルイソシアネートを適するアルコールと反応させる
ことにより、或いは適するベンズアミドを塩基の存在下
に適するクロル蟻酸のエステルと反応させることにより
自体公知の方法で得られると記載されている(第3頁、
第26〜28行〕。These pN-benzoyl-carbamates are stated to be obtainable in a manner known per se by reacting a suitable benzoyl isocyanate with a suitable alcohol or by reacting a suitable benzamide with a suitable ester of chloroformic acid in the presence of a base. (Page 3,
Lines 26-28].
今回驚くことに、一方ではベンゾイルイソシアネートの
使用を回避すると共に他方ではクロル蛾酸エステルの使
用を回避する経路により、N−ベンゾイルカルバメート
を高収率で製造しうることが突き止められた。It has now surprisingly been found that N-benzoyl carbamates can be prepared in high yields by a route which avoids the use of benzoyl isocyanate on the one hand and chloromace acid ester on the other hand.
したがって本発明によれば、−m式
〔式中、R1は水素原子、ハロゲン原子、cl−4アル
キル基、C1−4アルコキシ基もしくはトリフルオロメ
チル基を示し、Rzはハロゲン原子、Cl−4アルキル
基、C1−4アルコキシ基もしぐはトリ、フルオロメチ
ル基を示し、R3は水素原子、ハロゲン原子、メチル基
もしくはトリフルオロメチル基を示し、かっRは適宜1
個もしくはそれ以上のハロゲン原子により置換されたC
+−aアルキル基または適宜ハロゲン原子およびメチル
基から選択される1個もしくはそれ以上の置換基により
置換されたフェニル基を示す〕のN−ベンゾイルカルバ
メートを製造するに際し、−数式
〔式中、R1、RtおよびR3は上記の意味を有する〕
のベンズアミドのアルカリ金属塩を不活性溶剤の存在下
に式
%式%([)
〔式中、Rは上記の意味を有する〕
のカーボネー計と反応させ、かつ得られた式Iの化合物
のアルカリ金属塩を中和することを特徴とするN−ベン
ゾイルカルバメートの製造方法が提供される。Therefore, according to the present invention, -m formula [wherein R1 represents a hydrogen atom, a halogen atom, a Cl-4 alkyl group, a C1-4 alkoxy group, or a trifluoromethyl group, and Rz represents a halogen atom, a Cl-4 alkyl group] group, C1-4 alkoxy group or tri- or fluoromethyl group, R3 represents a hydrogen atom, halogen atom, methyl group or trifluoromethyl group, and R is 1 as appropriate.
C substituted by one or more halogen atoms
+-a represents an alkyl group or a phenyl group optionally substituted with one or more substituents selected from a halogen atom and a methyl group]. , Rt and R3 have the abovementioned meanings] in the presence of an inert solvent with a carbonate of the formula % ([) [wherein R has the abovementioned meanings] and neutralizing the alkali metal salt of the compound of formula I obtained.
式!および■において、R1は水素、弗素もしくは塩素
原子であり、R1は弗素もしくは塩素原子であり、かつ
R3は水素原子であることが好ましい、特に好適には、
R1およびR1は両者とも弗素原子である。formula! In and (2), R1 is hydrogen, fluorine or chlorine atom, R1 is fluorine or chlorine atom, and R3 is preferably hydrogen atom, particularly preferably,
Both R1 and R1 are fluorine atoms.
式!および■において、Rは好ましくはCI−6アルキ
ル基、便利にはC1−、アルキル基、たとえばメチルも
しくはエチル、或いはフェニル基である。formula! In and (2), R is preferably a CI-6 alkyl group, conveniently a C1-, an alkyl group such as methyl or ethyl, or a phenyl group.
式IIの化合物は上記英国特許第1,324.293号
、米国特許第4,457.943号、ヨーロッパ特許出
IIEP−A−161019号、BP−A−17427
4号、EP−A−219460号もしくは英国特許出1
11GB−A−2163430号各公報に記載されたよ
うに公知化合物であるか、或いはこれら公知化合物を製
造するために用いられる方法と同様な方法で製造するこ
とができる。Compounds of formula II are described in the above-mentioned British Patent No. 1,324.293, US Pat.
No. 4, EP-A-219460 or British Patent No. 1
It is a known compound as described in 11GB-A-2163430, or it can be produced by a method similar to the method used to produce these known compounds.
弐mの化合物も公知化合物であるか、或いはこれら公知
物質を製造するための方法と同様にして製造することが
できる。たとえばジメチルカーボネート、ジエチルカー
ボネート、ジフェニルカーボネートおよびジプロピルカ
ーボネートは、たとえばベルギー国、ブラッセル在アル
ドリッチ・ヘミーN、V、社から市販されている。Compound 2m is also a known compound, or can be produced in the same manner as the method for producing these known substances. For example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and dipropyl carbonate are commercially available, for example from Aldrich Chemie N, V, Brussels, Belgium.
式IIのベンズアミドのアルカリ金属塩は、便利にはア
ルカリ金属塩基、たとえばアルカリ金属(好ましくはリ
チウム、ナトリウムもしくはカリウム)の水素化物もし
くは水酸化物を用いてベンズアミドから生成することが
できる。溶剤の混合物としうる不活性溶剤の性質に応じ
、アルカリ金属塩は成る場合にはアルカリ金属自身から
その場で生成させることができる。Alkali metal salts of benzamides of formula II can be conveniently prepared from benzamides using alkali metal bases, such as hydrides or hydroxides of alkali metals (preferably lithium, sodium or potassium). Depending on the nature of the inert solvent, which may be a mixture of solvents, the alkali metal salt can be formed in situ from the alkali metal itself, if any.
最適反応温度は、特に弐mのカーボネートの性質および
不活性溶剤の性質に依存する。反応は便利にはO℃〜反
応混合物の蒸留温度の範囲の温度で行なうことができる
。The optimum reaction temperature depends, inter alia, on the nature of the carbonate and on the nature of the inert solvent. The reaction may conveniently be carried out at a temperature ranging from 0° C. to the distillation temperature of the reaction mixture.
適する不活性溶剤は、たとえばアセトンおよびメチルエ
チルケトンのようなケトン類、たとえば酢酸エチルのよ
うなエステル類、たとえば2−ブタノールのような第二
級アルコール、たとえばジクロルエタンもしくは塩化メ
チレンのような塩素化炭化水素、たとえばテトラヒドロ
フランのようなエーテル類、たとえばシクロヘキサンの
ような脂肪族炭化水素、並びにたとえばベンゼン、トル
エン、キシレンもしくはクロルベンゼンのような芳香族
溶剤である。Suitable inert solvents are, for example, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, secondary alcohols such as 2-butanol, chlorinated hydrocarbons such as dichloroethane or methylene chloride, For example, ethers such as tetrahydrofuran, aliphatic hydrocarbons such as cyclohexane, and aromatic solvents such as benzene, toluene, xylene or chlorobenzene.
好ましくは、弐■の化合物と式IIの化合物とのモル比
は1:1〜2:lである。Preferably, the molar ratio of the compound 2) to the compound of formula II is from 1:1 to 2:1.
不活性溶剤が第二級アルコールでない場合には、たとえ
ばイソプロパツール、第三級ブタノールもしくはりシル
イン酸のような第二級もしくは第三級ヒドロキシ化合物
の少量を添加して反協を開始させるのが有利であると判
明した。If the inert solvent is not a secondary alcohol, a small amount of a secondary or tertiary hydroxy compound such as isopropanol, tertiary butanol or polycylic acid may be added to initiate the reaction. turned out to be advantageous.
反応体を混合する順序は一般に臨界的でない。The order in which the reactants are mixed is generally not critical.
しかしながら、式IIのベンズアミドのアルカリ金属塩
を生成させるべく使用するアルカリ金属塩基が水酸化物
である場合は、この塩基を式IIの化合物に添加すると
共に、弐■の化合物の添加前に水を除去する。好ましく
は、アルカリ金属塩基と式Hの化合物とのモル比はl:
1〜1.5:1である。However, if the alkali metal base used to form the alkali metal salt of the benzamide of formula II is a hydroxide, then the base is added to the compound of formula II and water is added before addition of the compound of formula II. Remove. Preferably, the molar ratio of alkali metal base to compound of formula H is l:
The ratio is 1 to 1.5:1.
所望ならば式Iの化合物のアルカリ金属塩を単離するこ
とができ、或いはこれらを単離せずに中和することもで
きる。If desired, the alkali metal salts of the compounds of formula I can be isolated, or they can be neutralized without isolation.
得られた式lを有する化合物のアルカリ金属塩の中和は
、便利にはこの塩を酸水溶液(たとえば塩酸、硫酸、蟻
酸もしくは酢酸の水溶液)で処理して行なうことができ
る。中和は、便利には室温〜反応混合物の蒸留温度の範
囲の温度で行なうことができる。Neutralization of the alkali metal salt of the compound of formula I obtained can be conveniently carried out by treating the salt with an aqueous acid solution, for example an aqueous solution of hydrochloric acid, sulfuric acid, formic acid or acetic acid. Neutralization can be conveniently carried out at a temperature ranging from room temperature to the distillation temperature of the reaction mixture.
さらに本発明は、−数式
〔式中、Mはリチウム、ナトリウムもしくはカリウム原
子であり、かつR1、Rz 、R3およびRは上記の意
味を有する〕
のN−ベンゾイルカルバメートのアルカリ金属塩自身を
も提供する。Furthermore, the present invention also provides an alkali metal salt of N-benzoyl carbamate itself of the formula: do.
〔実臘例]
以下、例示の目的で本発明を実施例によりさらに説明す
る。[Examples] The present invention will now be further described by way of examples for illustrative purposes.
2.6−シフルオロベンズアミド(79,5g。2.6-cyfluorobenzamide (79.5 g.
0.5モル)とジメチルカーボネート(67g、0゜7
6モル)とアセトン(250d)とをO″Cにて−II
に攪拌し、水素化ナトリウム(16,6g、0゜69モ
ル)を添加した。反応を水素の回収および測定により監
視した。13j!の水素を回収しながら2時間の後、反
応混合物を室温(20°C)まで加温し、かつ水素の発
生が止まった後、蟻酸(98%、35g)を添加した。0.5 mol) and dimethyl carbonate (67 g, 0°7
6 mol) and acetone (250d) at O″C -II
The mixture was stirred and sodium hydride (16.6 g, 0.69 mol) was added. The reaction was monitored by hydrogen recovery and measurement. 13j! After 2 hours with recovery of hydrogen, the reaction mixture was warmed to room temperature (20° C.) and after hydrogen evolution had ceased, formic acid (98%, 35 g) was added.
さらに水素が全体で151まで発生した。得られた混合
物を濾過して、沈殿した蟻酸ナトリウムを除去し、かつ
得られたアセトン溶液を蒸発させてN−2,6−シフル
オロペンゾイルー〇−メチルカルバメートを白色固体(
109g、97%、高性能液体クロマトグラフィー(H
PLC)による純度97.2%、残部はジベンズフルオ
ロアミドである)を得た。Furthermore, a total of 151 hydrogen atoms were generated. The resulting mixture was filtered to remove precipitated sodium formate and the resulting acetone solution was evaporated to yield N-2,6-cyfluoropenzoyl-〇-methylcarbamate as a white solid (
109g, 97%, high performance liquid chromatography (H
A product with a purity of 97.2% by PLC, the remainder being dibenzfluoramide) was obtained.
NMR,CDC15中、δ(ppm) :3.75、s
、3H; 6.95、m−2H;7.40、m−I
Hi 8.7、s、IH。NMR, CDC15, δ (ppm): 3.75, s
, 3H; 6.95, m-2H; 7.40, m-I
Hi 8.7, s, IH.
て−緒に攪拌した。水素化ナトリウム(16,6g、0
.69モル)を添加し、次いでイソプロパツール(30
g)を添加して水素の発生を開始させた。The mixture was stirred together. Sodium hydride (16,6g, 0
.. 69 mol) and then isopropanol (30 mol).
g) was added to initiate hydrogen evolution.
反応を実施例1におけると同様に水素の回収および測定
により監視した。0°Cにて水素の発生が止まった後、
反応混合物を室温(20°C)まで加温し、かつ蟻酸(
35g)を添加した。水素の発生が止まり、かつ濾過し
て沈殿した蟻酸ナトリウムを除去し、溶剤を蒸発除去し
て粗生成物を白色固体(106g)として得た。この粗
生成物を1701dのトルエンに添加し、かつ透明溶液
が得られるまで加温した。室温まで冷却すると、白色固
体が沈殿し、これを濾過して純粋なN−2,6−シフル
オロベンゾイルー〇−メチルカルバメート(92g、8
5.5%)を得た: m、p、123〜123.5℃
。The reaction was monitored as in Example 1 by hydrogen recovery and measurement. After hydrogen generation stopped at 0°C,
The reaction mixture was warmed to room temperature (20°C) and formic acid (
35g) was added. Hydrogen evolution ceased and the precipitated sodium formate was removed by filtration and the solvent was evaporated to give the crude product as a white solid (106 g). This crude product was added to 1701d of toluene and warmed until a clear solution was obtained. Upon cooling to room temperature, a white solid precipitated and was filtered to give pure N-2,6-cyfluorobenzoyl-0-methylcarbamate (92 g, 8
5.5%) was obtained: m, p, 123-123.5°C
.
2.6−シフルオロベンズアミド(79,5g。2.6-cyfluorobenzamide (79.5 g.
0.5モル)とジメチルカルバメート(67g、0゜7
6モル)と酢酸エチル(250d)とを0°Cに2.6
−シフルオロペンズアミド(79g、0.5モル)とジ
メチルカルバメート(65g、0.72モル)と1.2
−ジクロルエタン(250II&)とを室温(20″C
)にて−緒に攪拌し、かつ水素化ナトリウム(16,8
g、0.7モル)を添加し、次いでイソプロパツール(
30g)を添加して水素の発生を開始させた。この混合
物を0℃まで冷却し、かつ反応を実施例1におけるよう
に水素の回収および測定により監視した。最初の10f
fiの水素を回収している間、反応混合物の激しい起泡
が観察された。 12.3ffiの水素が発生して反
応が停止した後、蟻酸を添加しかつ反応混合物を還流温
度まで加熱した。水素の発生が停止しかつ濾過(80°
C)して沈殿した蟻酸ナトリウムを除去した後、溶剤を
蒸発除去して粗生成物を白色固体(106g、HPLC
による純度94%)を得た。0.5 mol) and dimethyl carbamate (67 g, 0°7
6 mol) and ethyl acetate (250d) at 0°C.
- cyfluoropenzamide (79 g, 0.5 mol) and dimethyl carbamate (65 g, 0.72 mol) and 1.2
-dichloroethane (250II &) at room temperature (20″C)
) and sodium hydride (16,8
g, 0.7 mol) and then isopropanol (
30 g) was added to initiate hydrogen evolution. The mixture was cooled to 0° C. and the reaction was monitored by hydrogen recovery and measurement as in Example 1. first 10f
During the recovery of fi hydrogen, intense foaming of the reaction mixture was observed. After the reaction had stopped with evolution of 12.3ffi of hydrogen, formic acid was added and the reaction mixture was heated to reflux temperature. Hydrogen generation stops and filtration (80°
After removing the precipitated sodium formate in step C), the solvent was evaporated off and the crude product was purified as a white solid (106 g, HPLC
purity of 94%) was obtained.
トルエン(170d)から再結晶化して、純粋なN−2
,6−シフルオロベンゾイルー〇−メチルカルバメート
(99,7g、93%)を得た: m。Recrystallized from toluene (170d) to obtain pure N-2
,6-cyfluorobenzoyl-〇-methylcarbamate (99.7 g, 93%) was obtained: m.
P、123〜123.5°C0 l立桝土 N−−ジ ル ロベン゛ ルー〇− 2,6−シフルオロペンズアミド(79,2g。P, 123~123.5°C0 l standing masu soil N--Jill Robben Lou- 2,6-cyfluoropenzamide (79.2 g.
0.5モル)とジメチルカーボネート(65g、0゜7
2モル)と2−ブタ/−ル(250d)とを0°Cにて
一緒に攪拌し、かつ水素化ナトリウム(16,8g、0
.7モル)を添加した。121の水素が発生して反応が
停止した後、反応混合物を室温(20℃)まで加温し、
かつ蟻酸(32,5g)を添加した。濃厚スラリーの形
態にある混合物を80°Cまで加熱しかつ濾過して(8
0″c)、沈殿した蟻酸ナトリウムを除去した。溶剤を
蒸発させて、粗生成物を白色固体(111g、HPLC
による純度91.7%)として得た。トルエン(170
m)から再結晶化して、純粋なN−2,6−シフルオロ
ベンゾイルー〇−メチルカルバメート(87g。0.5 mol) and dimethyl carbonate (65 g, 0°7
2 mol) and 2-butyl (250 d) were stirred together at 0 °C and sodium hydride (16.8 g, 0
.. 7 mol) was added. After the reaction stopped with the evolution of hydrogen 121, the reaction mixture was warmed to room temperature (20 °C),
And formic acid (32.5 g) was added. The mixture in the form of a thick slurry was heated to 80°C and filtered (80°C).
0″c), the precipitated sodium formate was removed. The solvent was evaporated and the crude product was reduced to a white solid (111 g, HPLC
Purity: 91.7%). Toluene (170
Recrystallization from m) gave pure N-2,6-cyfluorobenzoyl-〇-methylcarbamate (87 g.
81%)を得た: m、p、123〜123.5°C
。81%) was obtained: m, p, 123-123.5°C
.
ルカルバ − の1゛1
ジフルオロベンズアミド(79g、0.5モル)とジメ
チルカーボネート(73g、0.8モル)とテトラヒド
ロフラン(200m)とを室温(20℃)にて−緒に攪
拌し、かつ水素化ナトリウム(16g、0.67モル)
を添加した0次いで、混合物を0℃まで冷却し、かつイ
ンプロパツール(30g)を添加して反応を開始させた
。12分間以内に12ffiの水素が発生した後、1時
間以内に13.21に達した。反応が停止した後、反応
混合物を室温(20°C)まで加温し、蟻酸(31,2
g)を添加した。この混合物を50℃まで加温し、室温
(20°C)まで冷却し、かつ濾過して沈殿した蟻酸ナ
トリウムを除去した。得られた濾液を蒸発させてN−2
,6−シフルオロペンゾイルー〇−メチルカルバメート
を白色固体(109g、97%、HPLCによる純度9
7%、残部はジフルオロベンズアミドである)を得た。Difluorobenzamide (79 g, 0.5 mol), dimethyl carbonate (73 g, 0.8 mol) and tetrahydrofuran (200 ml) were stirred together at room temperature (20°C) and hydrogenated. Sodium (16g, 0.67mol)
The mixture was then cooled to 0° C. and Improper Tool (30 g) was added to start the reaction. After 12ffi of hydrogen evolved within 12 minutes, 13.21 was reached within 1 hour. After the reaction has stopped, the reaction mixture is warmed to room temperature (20 °C) and formic acid (31,2
g) was added. The mixture was warmed to 50°C, cooled to room temperature (20°C) and filtered to remove precipitated sodium formate. The obtained filtrate was evaporated to N-2
,6-cyfluoropenzoyl-〇-methylcarbamate as a white solid (109 g, 97%, purity 9 by HPLC).
7%, the remainder being difluorobenzamide).
NMR,、CDC1!s中、σ(ppm) :3.75
、S、3H86,95、rn、 2 Hニア、40、m
11 H: 8.7、s、LHs実J実生1
116−ジフルオロベンズアミド(79g、0゜5モル
)とジメチルカーボネート(56g、0.6モル)とキ
シレン(400m)とを室温(20°C)にて−緒に攪
拌し、水素化ナトリウム(13g、0.54モル)を添
加した。イソプロパツール(45g)を添加して反応を
開始させ、かつ反応混合物をO′Cまで冷却し、そして
水素の発生が止まるまで0℃にて20時間攪拌した(1
22の水素が発生)、この反応混合物を室温(20”C
)まで加温し、かつ濾過した。得られた白色固体をキシ
レン(50s!x3)で洗浄し、次いでシクロヘキサン
(5Qal!X3)で洗浄してN−2,6−シフルオロ
ペンゾイルー〇−メチルカルバメート・ナトリウム塩(
120g、99%)を得た。NMR,, CDC1! In s, σ (ppm): 3.75
,S,3H86,95,rn, 2H near, 40,m
11 H: 8.7, s, LHs Seedling 1 116-difluorobenzamide (79 g, 0.5 mol), dimethyl carbonate (56 g, 0.6 mol) and xylene (400 m) were heated to room temperature (20°C). The mixture was stirred at room temperature and sodium hydride (13 g, 0.54 mol) was added. The reaction was started by adding isopropanol (45 g) and the reaction mixture was cooled to O'C and stirred for 20 h at 0 C until hydrogen evolution stopped (1
22 hydrogen evolution), and the reaction mixture was heated to room temperature (20"C).
) and filtered. The resulting white solid was washed with xylene (50s! x 3) and then with cyclohexane (5Qal!
120 g, 99%) was obtained.
NMRSD、アセトン中、δ (ppm) :3.44
、s−3H; 6.80、m、2HH7,20、m、
IH。NMRSD, in acetone, δ (ppm): 3.44
,s-3H;6.80,m,2HH7,20,m,
IH.
このナトリウム塩を酢酸もしくは塩酸に添加して(それ
ぞれの場合、室温(20°C)にて10w/W%の酸水
溶液400yd) 、N−2,6−シフルオロヘンゾイ
ルー〇−メチルカルバメー14定量的収率で得た:
m、p、123〜1215℃。This sodium salt was added to acetic acid or hydrochloric acid (in each case 400 yd of 10 w/w % aqueous acid solution at room temperature (20°C)) to form N-2,6-cyfluorohenzoyl-〇-methylcarbame 14. Obtained in quantitative yield:
m, p, 123-1215°C.
2.6−ジフルオロベンズアミド(48g、0゜3モル
)とジフェニルカーボネート(96g、0゜45モル)
とトルエン(400g)とを10゛cにて一緒に攪拌し
、水素化ナトリウム(8g、0.33モル、鉱油中の水
素化ナトリウムの50w/w%分散物として16g)を
添加した0反応部合物の温度は44°Cまで自然に上昇
し、この混合物は固体物質まで完全に成長した。反応混
合物の温度が降下し始めた後、沈殿固体を濾別してN−
2゜6−ジフル矛ロペンゾイルー0−フェニルカルバメ
ート・すトリウム塩〔混N[(gull)にお1するI
Rスペクトル(cm−’): 3450ブロード小、
3400ブロード小、2740シヤープ小、2680シ
ヤープ小、1690ブロード大、1630シヤープ小、
1550ブロード大、1240シヤープ小、1170ブ
ロード大、1115ブロード中、1005シヤープ小、
970シヤープ小、905シヤープ中、810シヤープ
小、765シツルダー、725シヤープ中、695シヤ
ープ中〕を得た。2.6-difluorobenzamide (48g, 0°3 mol) and diphenyl carbonate (96g, 0°45 mol)
and toluene (400 g) were stirred together at 10 °C and sodium hydride (8 g, 0.33 mol, 16 g as a 50 w/w % dispersion of sodium hydride in mineral oil) was added. The temperature of the compound rose spontaneously to 44°C and the mixture grew completely to a solid material. After the temperature of the reaction mixture begins to drop, the precipitated solids are filtered off and N-
2゜6-difluorophenzoyl-0-phenylcarbamate sodium salt [I added to mixed N [(gull)]
R spectrum (cm-'): 3450 broad small,
3400 broad small, 2740 sharp small, 2680 sharp small, 1690 broad large, 1630 sharp small,
1550 broad large, 1240 sharp small, 1170 broad large, 1115 broad medium, 1005 sharp small,
970 sharp small, 905 sharp medium, 810 sharp small, 765 sharp, 725 sharp medium, 695 sharp medium] were obtained.
この塩をlQw/w%酢酸水溶液(400d)中で室温
にて攪拌することにより、N−2,6−シフルオロペン
ゾイルー〇−フェニルカルバメート(80g、95%)
を得た: m、p、149°C02,6−ジフルオロ
ベンズアミド(48g、0゜3モル)とジエチルカーボ
ネート(45g、0.4モル)とシクロヘキサン(25
0d)とを室温にて一緒に攪拌し、水素化ナトリウム(
7,5g、031モル)を添加した。ワシノ1/・イン
酸、【0.5g)を添加して、反応を開始させた1次い
でこの反応混合物を室温(20°C)にて72時間攪拌
し、次いで沈殿した固体物質を濾過し、かつシクロヘキ
サンで洗浄してN−2,6−シフルオロベンゾイルー〇
−エチルカルバメート・ナトリウム塩〔混雑(+all
)におけるIRスペクトル(C1l−’): 335
0ブロード小、3300ブロード小、3150ブロード
小、1650 N1500多重ピーク、1225ブロー
ド大、1135ブロード中、1045シヤープ小、10
00シヤープ中、970シヤープ中、935ブロード中
、800〜700多重ピーク]を得た。By stirring this salt in lQw/w% aqueous acetic acid solution (400d) at room temperature, N-2,6-cyfluoropenzoyl-〇-phenylcarbamate (80g, 95%) was obtained.
Obtained: m, p, 149°C02,6-difluorobenzamide (48 g, 0.3 mol), diethyl carbonate (45 g, 0.4 mol) and cyclohexane (25
0d) and stirred together at room temperature, sodium hydride (
7.5 g, 0.31 mol) was added. The reaction was started by the addition of Wasino 1/-inic acid, 0.5 g).The reaction mixture was then stirred at room temperature (20 °C) for 72 hours, and the precipitated solid material was then filtered. and washed with cyclohexane to remove N-2,6-cyfluorobenzoyl-ethylcarbamate sodium salt [congested (+all
) IR spectrum (C1l-'): 335
0 small broad, 3300 small broad, 3150 small broad, 1650 N1500 multiple peaks, 1225 large broad, 1135 medium broad, 1045 small sharp, 10
00 sharp, 970 sharp, 935 broad, 800-700 multiple peaks] were obtained.
実施例7におけると同様な酢酸水溶液での処理はN−2
,6−シフルオロペンゾイルー〇−エチルカルバメート
(57g、83%)を与えた二m、p、105℃。Treatment with aqueous acetic acid similar to that in Example 7 resulted in N-2
, 6-cyfluoropenzoyl-〇-ethylcarbamate (57 g, 83%) at 2 m, p, 105°C.
2.6−シフルオロペンズアミド(48g、0.3モル
)ト水酸化カリウムのペレット(19,68g。2.6-cyfluoropenzamide (48 g, 0.3 mol) and potassium hydroxide pellets (19.68 g).
85.5%)とオレイン酸(1,38g)とトルエンと
の混合物を1.5時間にわたり共沸蒸留にがけた。A mixture of oleic acid (1.38 g) and toluene was subjected to azeotropic distillation for 1.5 hours.
ジフェ、−ルカーボネート(66g、 0.31 モ/
L+)を添加し、かつ蒸留温度にてさらに15分間の後
、混合物を室温まで冷却した。沈殿した固体を反応混合
物から濾別し、かつ実施例7におけると同様に酢酸水溶
液で処理してN−2,6−シフルオロペンゾイルー〇−
フェニルカルバメート(64g。dife, -carbonate (66 g, 0.31 mo/
After addition of L+) and a further 15 minutes at distillation temperature, the mixture was cooled to room temperature. The precipitated solid was filtered from the reaction mixture and treated with aqueous acetic acid as in Example 7 to give N-2,6-cyfluoropenzoyl-
Phenyl carbamate (64g.
77元)を得た: m、p、149℃。77 yuan) was obtained: m, p, 149°C.
実施例9におけると同様な手順を用いたが水酸化カリウ
ムの代わりに水酸化リチウムを用いて、N−2,6−シ
フルオロペンゾイルー〇−エチルカルバメート・リチウ
ム塩を介しN−2,6−シフルオロペンゾイルー〇−エ
チルカルバメート(m、p、105°C)を製造した。Using a similar procedure as in Example 9 but using lithium hydroxide in place of potassium hydroxide, N-2,6-cyfluoropenzoyl--ethylcarbamate lithium salt was -cyfluoropenzoyl-〇-ethyl carbamate (m, p, 105°C) was prepared.
〔混雑(mull)におけるrRスペクトル(cm−’
): 3350ブロード中、3180ブロード中、1
650〜15001500多、!250ブロード大゛、
1155ブロード小、1120ブロード小、1050ブ
ロード小、1000シヤープ中、955シッルダ−88
0シヤープ小、810〜690多重の小および中ピーク
]。[rR spectrum in mull (cm-'
): 3350 broad, 3180 broad, 1
650~15001500 more! 250 broad,
1155 Broad Small, 1120 Broad Small, 1050 Broad Small, 1000 Sharp Medium, 955 Shielder-88
0 sharp small, 810-690 multiplex small and medium peaks].
中、191シa)Ltダー、750シ+−7’中、71
5シヤープ中〕。Medium, 191 Shear) Lt Dar, 750 Shi+-7' Medium, 71
5 sharp].
Claims (8)
_4アルキル基、C_1_−_4アルコキシ基もしくは
トリフルオロメチル基を示し、R^2はハロゲン原子、
C_1_−_4アルキル基、C_1_−_4アルコキシ
基もしくはトリフルオロメチル基を示し、R^3は水素
原子、ハロゲン原子、メチル基もしくはトリフルオロメ
チル基を示し、かつRは適宜1個もしくはそれ以上のハ
ロゲン原子により置換されたC_1_−_8アルキル基
または適宜ハロゲン原子およびメチル基から選択される
1個もしくはそれ以上の置換基により置換されたフェニ
ル基を示す〕のN−ベンゾイルカルバメートを製造する
に際し、一般式 ▲数式、化学式、表等があります▼(II) 〔式中、R^1、R^2およびR^3は上記の意味を有
する〕 のベンズアミドのアルカリ金属塩を不活性溶剤の存在下
に式 RO−CO−OR(III) 〔式中、Rは上記の意味を有する〕 のカーボネートと反応させ、かつ得られた式 I の化合
物のアルカリ金属塩を中和することを特徴とするN−ベ
ンゾイルカルバメートの製造方法。(1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is a hydrogen atom, a halogen atom, C_1_-
_4 alkyl group, C_1_-_4 alkoxy group or trifluoromethyl group, R^2 is a halogen atom,
C_1_-_4 alkyl group, C_1_-_4 alkoxy group or trifluoromethyl group, R^3 represents a hydrogen atom, halogen atom, methyl group or trifluoromethyl group, and R appropriately represents one or more halogens. When producing N-benzoyl carbamate of the general formula [C_1_-_8 represents an alkyl group substituted by an atom or a phenyl group optionally substituted by one or more substituents selected from a halogen atom and a methyl group] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1, R^2 and R^3 have the above meanings] In the presence of an inert solvent, an alkali metal salt of benzamide of the formula N-benzoyl, characterized in that it is reacted with a carbonate of RO-CO-OR (III) [wherein R has the above meaning] and the resulting alkali metal salt of the compound of formula I is neutralized. Method for producing carbamates.
^2が弗素もしくは塩素原子であり、かつR^3が水素
原子である請求項1記載の方法。(2) R^1 is hydrogen, fluorine or chlorine atom, and R
2. The method according to claim 1, wherein ^2 is a fluorine or chlorine atom, and R^3 is a hydrogen atom.
求項1記載の方法。(3) The method according to claim 1, wherein R^1 and R^2 are both fluorine atoms.
基である請求項1、2または3記載の方法。(4) The method according to claim 1, 2 or 3, wherein R is a C_1_-_6 alkyl group or a phenyl group.
物もしくは水酸化物を用いて式IIのベンズアミドの塩を
生成させる請求項1〜4のいずれか一項に記載の方法。5. A process according to claim 1, wherein a hydride or hydroxide of lithium, sodium or potassium is used to form the salt of the benzamide of formula II.
で行なう請求項1〜5のいずれか一項に記載の方法。(6) The method according to any one of claims 1 to 5, wherein the reaction is carried out at a temperature ranging from 0°C to the distillation temperature of the reaction mixture.
子であり、かつR^1、R^2、R^3およびRは請求
項1〜4のいずれか一項に記載の意味を有する〕 のN−ベンゾイルカルバメートのアルカリ金属塩。(7) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, M is a lithium, sodium or potassium atom, and R^1, R^2, R^3 and R are claims An alkali metal salt of N-benzoyl carbamate having the meaning as defined in any one of 1 to 4 above.
製造された式 I のN−ベンゾイルカルバメート。(8) N-benzoyl carbamate of formula I produced by the method according to any one of claims 1 to 6.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898905741A GB8905741D0 (en) | 1989-03-13 | 1989-03-13 | Process for preparing carbamates,and intermediates therin |
GB8905741.8 | 1989-03-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02279666A true JPH02279666A (en) | 1990-11-15 |
Family
ID=10653242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2056796A Pending JPH02279666A (en) | 1989-03-13 | 1990-03-09 | Production of carbamate and its intermediate |
Country Status (16)
Country | Link |
---|---|
US (1) | US5189197A (en) |
EP (1) | EP0387946B1 (en) |
JP (1) | JPH02279666A (en) |
KR (1) | KR0168664B1 (en) |
CN (1) | CN1028523C (en) |
AT (1) | ATE101595T1 (en) |
BR (1) | BR9001139A (en) |
CA (1) | CA2011856A1 (en) |
DD (1) | DD298779A5 (en) |
DE (1) | DE69006607T2 (en) |
DK (1) | DK0387946T3 (en) |
ES (1) | ES2062291T3 (en) |
GB (1) | GB8905741D0 (en) |
HU (1) | HU207989B (en) |
IE (1) | IE63466B1 (en) |
RU (1) | RU2033410C1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018095576A (en) * | 2016-12-09 | 2018-06-21 | 学校法人 名城大学 | Salt of isolated compound containing amide group, method for producing the same, and method for synthesizing amide compound using the same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2308564A1 (en) * | 2000-05-15 | 2001-11-15 | Mark J. Frazer | Communication structure for multiplexed links |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL160809C (en) * | 1970-05-15 | 1979-12-17 | Duphar Int Res | METHOD FOR PREPARING BENZOYLURUM COMPOUNDS, AND METHOD FOR PREPARING INSECTICIDE PREPARATIONS BASED ON BENZOYLURUM COMPOUNDS. |
EP0052833B1 (en) * | 1980-11-22 | 1983-12-14 | CELAMERCK GmbH & Co. KG | Urea derivatives, preparation and use |
US4595533A (en) * | 1982-09-23 | 1986-06-17 | Ppg Industries, Inc. | Method for producing N-organocarbamates and N,N-bis(organo)carbamates |
CA1339745C (en) * | 1984-04-10 | 1998-03-17 | Martin Anderson | Pesticidal benzoylurea compounds |
JPS60215660A (en) * | 1984-04-11 | 1985-10-29 | Nippon Tokushu Noyaku Seizo Kk | Preparation of biphenylsulfonylurea derivative, intermediate therefor and preparation of said intermediate |
ATE50245T1 (en) * | 1984-08-24 | 1990-02-15 | Ciba Geigy Ag | BENZOYLPHENYL UREAS. |
TR23048A (en) * | 1984-08-31 | 1989-02-14 | Ciba Geigy Ag | FENILBENZOILUERES, IMMEDIATE PROCEDURES AND THEIR USE FOR POSSIBILITY OF DAMAGES |
EP0219460B1 (en) * | 1985-10-14 | 1991-05-02 | Ciba-Geigy Ag | Benzoylphenyl ureas |
GB8714873D0 (en) * | 1987-06-25 | 1987-07-29 | Bp Chemicals Additives | Additives |
-
1989
- 1989-03-13 GB GB898905741A patent/GB8905741D0/en active Pending
-
1990
- 1990-02-27 US US07/485,550 patent/US5189197A/en not_active Expired - Fee Related
- 1990-03-06 EP EP90200534A patent/EP0387946B1/en not_active Expired - Lifetime
- 1990-03-06 DK DK90200534.7T patent/DK0387946T3/en active
- 1990-03-06 ES ES90200534T patent/ES2062291T3/en not_active Expired - Lifetime
- 1990-03-06 AT AT90200534T patent/ATE101595T1/en active
- 1990-03-06 DE DE69006607T patent/DE69006607T2/en not_active Expired - Fee Related
- 1990-03-07 RU SU904743555A patent/RU2033410C1/en active
- 1990-03-08 KR KR1019900003053A patent/KR0168664B1/en not_active IP Right Cessation
- 1990-03-09 IE IE86090A patent/IE63466B1/en not_active IP Right Cessation
- 1990-03-09 JP JP2056796A patent/JPH02279666A/en active Pending
- 1990-03-09 CN CN90101247A patent/CN1028523C/en not_active Expired - Fee Related
- 1990-03-09 CA CA002011856A patent/CA2011856A1/en not_active Abandoned
- 1990-03-09 BR BR909001139A patent/BR9001139A/en not_active Application Discontinuation
- 1990-03-09 DD DD90338553A patent/DD298779A5/en not_active IP Right Cessation
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Cited By (1)
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JP2018095576A (en) * | 2016-12-09 | 2018-06-21 | 学校法人 名城大学 | Salt of isolated compound containing amide group, method for producing the same, and method for synthesizing amide compound using the same |
Also Published As
Publication number | Publication date |
---|---|
ATE101595T1 (en) | 1994-03-15 |
CN1045579A (en) | 1990-09-26 |
ES2062291T3 (en) | 1994-12-16 |
HUT54111A (en) | 1991-01-28 |
CN1028523C (en) | 1995-05-24 |
KR900014290A (en) | 1990-10-23 |
DD298779A5 (en) | 1992-03-12 |
GB8905741D0 (en) | 1989-04-26 |
BR9001139A (en) | 1991-03-05 |
DK0387946T3 (en) | 1994-03-14 |
US5189197A (en) | 1993-02-23 |
HU207989B (en) | 1993-07-28 |
EP0387946A1 (en) | 1990-09-19 |
DE69006607D1 (en) | 1994-03-24 |
KR0168664B1 (en) | 1999-03-20 |
DE69006607T2 (en) | 1994-05-26 |
HU901377D0 (en) | 1990-05-28 |
IE63466B1 (en) | 1995-04-19 |
IE900860L (en) | 1990-09-13 |
CA2011856A1 (en) | 1990-09-13 |
RU2033410C1 (en) | 1995-04-20 |
EP0387946B1 (en) | 1994-02-16 |
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